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and rpreferably the preferentially water-soluble petroleum sulfonates obtained in the treatment of petroleum oils with a sulfonating agent such asv concentrated sulfuric acid or fuming sulfuric acid. Other suitable detergents are the alkylated aromatic sulfonates having from about to about Y 16 carbon atoms in the alkyl group, such as for ly with a number of portions of concentrated sulacids,j'which are referred to as detergent-type furie acid (i. e., above about 95%strength) or fuming sulfuric acid. The sulfuric acid is usual- Y ly added in "dumps of about 1A? pound per# gallon of oil, the total quantity of acid treated depending upon the oil being treated andthe desired final product. Usually from about 3 poundslto about 9 pounds of sulfuric acid Vper gallon ofoil is used. Some of the sulfonic acids resulting from the treatment of the oil withthe sulfuridacid are preferentially oil-soluble, a majorfproportion ofV which remain in the oil layerafter the removalv of the acid sludge resultin'gfromv the acid treatment of the oil. These can be Aremoved from the oil by neutralizingthe acid-treatedzoil with an alkaline agent,.such as ammonapor ari-alkali metal hydroxide, preferably sodiumfhydroxide, 'to form the corresponding sulfonic acid soaps vwhich are then extracted from the oil with 50% to. 80% aqueous alcohol solutions or other suitable means. Because of theircharacteristic mahogany colorVA these sul-v fonates are known in the petroleum art as mahogany soaps. They usually contain..about 35 to 50% of the true soap mixed with oil, some water and a small amount of salts, such as so dium sulfonate, `which are difficult to remove.` Y

While most ofthe preferentially oil-solublefsulfonates are obtained from lthe acid-treated-oil by neutralization with alkali, there can be recovered from the acid sludge by suitable solvents havinga viscosity within the range of about 55 to seconds Saybolt Universal viscosity aty100- F., with about'fourA poundsv of fuming sulfuric aciCLhave molecular weights of about 400 'to 410 andare the` least oil-soluble of the so-called mahogany acids, while the mahogany acids having molecular weights of about 470-500 are the most oil soluble and least water-soluble sulfonic acids. The alkalirrnetal soap, preferably sodium soap or the ammonia soap of these low molecular weight mahogany acids, namely those having molecular weights of about 400 to 410 are particularly well suited for use in the present. invention.

The alkali metal and ammonia soaps of petroleum sulfonate acids having molecular weights above 425-450 can be used inthe present invention, but preferably in combination with a preferentially water-soluble soap or detergent. For example, thesodium soap of-a mahogany acid having molecular weights of about 450-570 can 4 v be used in combination with sodium rosin soap, an alkylated aromatic sulfonate of 12 to 16 carbon atoms, or a preferentially Water-soluble petroleum sulfonate.

In addition to the mahogany soaps which are vusually recovered from the acid-treated oil, there is another class of sulfonic acids, recoverable from the acid sludge, resulting from the treatment of petroleum oils with sulfuric acid. These acid sludge sulfonic acids, which are generally referredY to as green acids because of their characteristic greenishl color, are preferentially water-soluble and have molecular weights of from about 430 to vabout 450. The green acids are mixturesV of very water-soluble sulfonic acids known asy black acids, intermediate water-soluble sulfonic acids andv preferentially oil-soluble sulfonicacids which are deep red tobrown in color and are usually referredto as' brown acids. The brown acids are less oil-soluble than the mahogany acids. The green acids can be recovered fromthe acid sludge by adding water to the sludge to dilute the Vsulfuric acid to a concentration of 20 to 30 percent at whichconcentration the green acids separate to forma supernatant layer. Alternatively,` the green acidscan bev extracted from the-sludge byusing water-soluble solvents or mixtures of organic solvents `with was ter. Thev detergent-type preferentially watersoluble acid sludgey can be recovered as suchf'rom the acid sludge by extraction'with benzene: or carbon tetrachloride, ormixtures thereof. The present inventionk contemplates .employing alkali metal or ammoniumgreen acidsoaps ordeter-A gent-'type acidsoaps in place of the soaps of low molecular weight mahogany acids or. mixtures or the preferentialY water-soluble sulfonates with the preferential oil-soluble sulfonates. For certain applications a mixture of :hydroformer bottoms and detergents Vis not suitable orpractical as it may have a. tendency 'to' remove paint from the painted surfaces to be cleaned of grease, oil, etc. Under these conditions,it `is advantageousto incorporate inthe mixture a diluent material such as a liquid .hydrocarbon, for example a Vpetroleum distillate having an initial boiling point above about 300 F.v Suitable petroleum distillates are those distilling within the distillation range of kerosene (approximately 300"V F to 550 F.), gas oil (about 400:F. yto ,750 F.) oleum spirits (about 300 F. to 430?"F.),A and similar petroleum fractions.

The followingexamples are illustrative of for-v mulations suitable for Athe herein-described pur-v poses:

Example I An emulsiable floor and driveway cleaner is prepared by mixing the followingV ingredients in theapproximate proportions by volume:

I l Per cent (v ol.) Sodium mahogany soap (35-50 true soap; 450- 470 molecularwt.) 13 `Sodium rosin soap 1 v 2 true soap; 400-410 molecular wt.) 15 Hydroformer bottoms (0-90% cut) 85 Example III Due to the high solvency effect of the hydroformer bottoms, the paint of painted floors and/or driveways to be cleaned of oil, etc., may be removed. A composition having the following formulations, while very elective for removing grease, oil, etc., will not remove paint from painted surfaces:

Per cent (vol.)

While the present invention has been described by reference to certain preferred embodiments thereof, it is to be understood that the same are given by way of illustration only and are not intended as limiting the scope of the invention, except as the same is defined by the following claims.

We claim:

1. An emulsiable :door and driveway cleaner comprising about 13 by volume of a sodium soap of a mahogany acid having a molecular weight of about 450 to about 470, about 2% by volume of a sodium rosin soap and about 85% by volume of a catalytic reformed naphtha bottoms boiling between about 400 F. to about 750 F.

, 2. A cleansing composition for removing grease and oil, comprising about 12.4% by volume of a sodium soap of a mahogany acid having a molecular Weight of about 400' to 410, about 40% by volume of a ninety percent cut of a catalytic reformed naphtha bottoms having a distillation range between about 400 F. to about 600 F. and about 47.6% by volume of a petroleum distillate having a distillation range of from about 340 F. toabout 510 F.

3. A cleansing composition comprising from about 10% to about 25%, by volume, of a detergent selected from the group consisting of a sodium soap of a mahogany acid having a molecular weight of about 400 to about 410, and a sodium soap of a mahogany acid having a molecular weight of about 450 to about 470 in combination with a sodium rosin soap, from about 5% to about 85%, by volume, of a catalytic reformed naphtha bottoms having a distillation range between about 400 F. and about 750 F., and up to about 85%, by volume, of a petroleum distillate having a distillation range of between about 300 F. to about 750 F.

JEROME W. ARKI-S.

DONALD IRVINE WALKER.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS 

1. AN EMULSIFIABLE FLOOR AND DRIVEWAY CLEANER COMPRISING ABOUT 13% BY VOLUME OF A SODIUM SOAP OF A MAHOGANY ACID HAVING A MOLECULAR WEIGHT OF ABOUT 450 TO ABOUT 470, ABOUT 2% BY VOLUME OF A SODIUM ROSIN SOAP AND ABOUT 85% BY VOLUME OF A CATALYTIC REFORMED NAPHTHA BOTTOMS BOILING BETWEEN ABOUT 400* F. TO ABOUT 750* F. 